title: [3:1] site-differentiated [4Fe-4S] clusters having one carboxylate and three thiolates.
abstract: [4Fe-4S] clusters modeled after those in organisms having three cysteine thiolates and one carboxylate were synthesized by using the tridentate thiolato chelate. X-ray structural analysis reveals that the carboxylates coordinate to the unique irons in an η(1) manner rather than η(2). Redox potentials show a positive shift from that of the cluster having ethanethiolate and the tridentate thiolato chelate. These properties conform to the arrangement of the [4Fe-4S] clusters in the electron transfer systems included in Rc dark operative protochlorophyllide oxidoreductase (DPOR) and formaldehyde oxidoreductase (FOR) with Pf ferredoxin.
authors.affiliation: Department of Chemistry, Graduate School of Science, ‡Institute of Transformative Bio-Molecules (WPI-ITbM), and §Research Center for Materials Science, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
authors.forename: Tamaki
authors.initials: T
authors.lastname: Terada
authors.forename: Kiyohisa
authors.initials: K
authors.lastname: Hirabayashi
authors.forename: Dong
authors.initials: D
authors.lastname: Liu
authors.forename: Tomohiko
authors.initials: T
authors.lastname: Nakamura
authors.forename: Takuya
authors.initials: T
authors.lastname: Wakimoto
authors.forename: Tsuyoshi
authors.initials: T
authors.lastname: Matsumoto
authors.forename: Kazuyuki
authors.initials: K
authors.lastname: Tatsumi
mesh_terms: D002264:Carboxylic Acids / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007506:Iron-Sulfur Proteins / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D002264:Carboxylic Acids; D007506:Iron-Sulfur Proteins; D013438:Sulfhydryl Compounds